Fungicidal composition



FUNGIC-IDAL COMPOSITION Thomas W. Sauls, College Park, Ga.,.assignor toTennessee Corporation, New York, N.Y., a corporation of New York NoDrawing. Application November 14, 1956 Serial No. 621,999

8 Claims. (Cl. 167-42) This invention relates to pesticidal andfungicidal compositions and more particularly to such compositions whichare intended or adapted to be dispersed in water for application toplants, fruit, or the like in the'form of a spray.

The fungitoxicity of certain metal salts of dodecylbenzene sulfonic acidis known. Difiiculty is sometimes en countered in. drying and handlingthese materials, butthey areefiective fungicides and desirableingredients of compositions of the type characterized above,particularly the salts of polyvalent metals such as barium, calcium,iron, manganese, copper, zinc, etc. Normal wet spray applications ofsuch compositions utilize aqueous dispersions which contain in theneighborhood of only 0.01% to 2.0 of the desired salt or salts. For usein wet sprays, therefore, good dispersibility in water is a necessityfor any such salt marketed or distributed in the form of a dry.composition, whereas the polyvalent metal salts of dodecylbenzenesulfonic acid are quite difficult todisperse in dilute aqueoussuspensions.

One of the principal objects of the present invention is to provide adry fungicidal composition which can be dispersed quickly and readily inaqueous liquid to form a wet spray containing one or more of theaforesaid polyvalent metal salts of dodecylbenzene sulfonic acid.

Another object is to simplify manufacturing and drying, problems and toeliminate the need'for definiteparticle size in the production of saidpolyvalent metal salts of dodecylbenzene sulfonic acid for use in dryfungicidal compositions.

A further object is to provide improved suspensions or dispersions ofsaid polyvalent metal salt or salts of do decylbenzene sulfonic acidwhich are superior to those heretofore obtainable with compositionscontaining the dried metal salts.

Other objects of the invention will appear hereinafter.

The foregoing objects are realized by the incorporation in dryfungicidal compositions of a dry mechanical mixture of the sodium and/orpotassium salts of dodecylbenzene sulfonic acid and one ormorewater-soluble salts of polyvalent metals. When the dry composition iseventually added to water, these ingredients dissolve and then react toform a precipitate of the desired polyvalent metal salt ofdodecylbenzene sulfonic acid. Thus problems of mechanically dispersingthe insoluble dry salt or salts in water are completely eliminated, andthe salt is formed in the aqueous liquid in the form of a very finelydivided precipitate which remains in suspension for a long time. Suchdispersions of polyvalent metal salts of dodecylbenzene sulfonic acidare substantially superior to those heretofore obtainable bymechanically dispersing the dried metal salt in aqueous medium.

It will be understood that in case it is desired to have a mixture ofsalts of different polyvalent metals in the spray,

tioned, the dry composition may include other materials adapted forspray application and inert towardthe reaction mentioned above, such asclays, fullers earth, etc.,- sticking agents, nutrients or fertilizers,various other types of pesticides or fungicides, etc.

The amount of polyvalent metal salt to be employed should preferably bethe stoichiometric equivalent of the amount of sodium and/ or potassiumdodecylbenzene sul-' fonate, in order that all or substantially all ofthe latter will be converted into the precipitate mentioned above.

If less than the equivalent amount is used, then some of the sodium orpotassium sulfonatewill remain in solution, whereas on the other handexcess polyvalent metal salt is simply wasted. Of course, two or moremetal ions can'be used if desired by simply combining two or morepolyvalent metal salts to makeup the desired total amount. The selectionof the metal ion or ions to be used will depend onconsiderations ofavailability and cost, except in cases where the characteristics and/orproperties of particular metal ions may make them preferred. Forexample, copper salts tend to be more phytotoxic, while less solublesalts such as the barium salt tend to be more resistant to washing offthe plants.

In addition to the considerations stated above, the choice of the metalion or ions to' be used may sometimes be determined' by special factors,for example, a need to supplement mineral deficiencies. Broadlyspeaking, however, any water-soluble salt or salts of any desiredpolyvalent metal or metals can be employed. The metals most commonlyused for the purposes of the invention include zinc, copper, barium,iron and manganese,

acetate, barium butyrate, barium cyanide, barium nitrate,

barimn propionate, manganese sulfate, manganese acctate, manganesechloride, managanese benzoate, manganese bromide, manganese nitrate,manganese silicoflu oride, ferrous sulfate, magnesium acetate, magnesiumchloride, magnesium nitrate, magnesium silicofluoride, calcium chloride,calicum acetate, calcium sulfate, lead acetate, lead nitrate, mercuricacetate, mercuric chloride, mercuric nitrate, etc.

By Way of example, stoichiometric equivalents of sodium dodecylbenzenesulfonate and zinc sulfate, together with a small amount of finelydivided synthetic calcium silicate such as Micro-Col, form a nice drymix when mixed with mortar and pestle or by equivalent simple mechanicaloperations. This mixture may be combined by any suitable mixingprocedure with other desired ingredients as already stated. Theresulting dry composition is simply bagged or filled into other desiredcontainers for storage and distribution. When it comes to actual use asa spray, the composition is simply added to water in the desiredproportion and the finely divided precipitate forms in the dispersion asalready explained. As already indicated, the amount of the drycomposition will usually be such as to provide a concentration ofpolyvalent metal salt of dodecylbenzene sulfonic acid in the dispersionwhich is in the approximate range of 0.01% to 2.0%.

In addition to its advantages in use, the invention further simplifiesthe production of the original sodium or potassium dodecylbenzenesulfonate in that no definite particle size is required for use in thedry fungicidal composition. A simple milling of the dried sulfonatesuflices to produce a stable, free-flowing material that can be typicalof compositions embodying the invention:

I. Dry mix formula:

38.6 parts 90% sodium dodecylbenzene sulfonate 1.5 parts syntheticcalcium silicate (+325 mesh) 9.0 parts zinc sulfate monohydrate 1.0 partlignin sulfonate II. Dry mix formula:

2010 parts 90% sodium dodecylbenzene sulfonate 214 parts copper sulfatepentahydrate powder 332 parts zinc sulfate monohydrate 81 partssynthetic calcium silicate (+325 mesh) III. Dry rnix formula:

38.6 parts 90% sodium dodecylbenzene sulfonate 9.0 parts zinc sulfatemonohydrate 15.8 parts synthetic calcium silicate (+325 mesh) IV. Drymix formula:

38.6 parts 90% sodium dodecyl benzene sulfonate 9.0 paits zinc sulfatemonohydrate 15.8 parts synthetic. calcium silicate (+325 mesh) 6.5 partscolloidal magnesium aluminum silicate V. Dry mix formula: V

3.86 parts 90% sodium dodecylbenzene sulfonate 1.22 parts bariumchloride-dihydrate VI. Dry mix formula:

3.86 parts 90% sodium dodecylbenzene sulfonate 0.86 part calcium sulfatedihydrate 1. A fungicidal composition adapted when mixed with water toform a wet spray containing a dispersed suspension of water-insolublepolyvalent metal salt of dodecylbenzene sulfonic acid as an activefungicidal ingredient, said composition comprising a dry, comminuted,substantially free-flowing physical mixture of a water-solubledodecylbenzene sulfonate of the group consisting of the sodium andpotassium sulfonates and a water-soluble polyvalent metal salt of thegroup consisting of the water-solu-- ble salts of zinc, copper, barium,iron, manganese, magnesium, calcium, lead and mercury, said mixturebeing packaged for distribution in the dry state and said sulfonate andsaid water-soluble metal salt having approximately stoichiometricproportions and adapted to react when added to water to form a stableaqueous suspension of a finely divided dispersed precipitate of saidwater-insol'uble metal salt of dodecyl benzene sulfonic acid.

2. A composition as defined in claim 1 including at least twowater-soluble salts of polyvalent metals.

3. A composition as defined in claim 1, said watersoluble metal saltbeing zinc sulfate.

4. A composition as defined in claim 1, said Watersoluble metal saltbeing manganese sulfate.

5. A composition as defined in claim 1, said watersoluble metal saltbeing cupric sulfate.

6. A composition as defined in claim 1, said watersoluble metal saltbeing ferrous sulfate.

7. A composition as defined in claim 1, said watersoluble metal saltbeing barium chloride.

8. The method of preparing a stable aqueous suspension of awater-insoluble polyvalent metal salt of dodecylbenzene sulfonic acidfor use as a wet fungicidal spray which comprises forming a dry,comminuted, substantially free-flowing physical mixture inapproximately. stoichiometric proportions of a water-solubledodecylbenzene sulfonate of the group consisting of the sodium andpotassium sulfonates and a water-soluble polyvalent metal salt of thegroup consisting of the water-soluble salts of zinc, copper, barium,iron, manganese, magnesium, calcium, lead and mercury, packaging saidmixture for distribution in dry form, and finally preparing the desiredwet spray for use by adding the appropriate amount of said dry mixtureto water, thereby causing a reaction between said sulfonate and saidwater-soluble metal salt to form said water-insoluble polyvalent metalsalt of dodecyl benzene sulfonic acid as a finely divided precipitate indispersed aqueous suspension.

References Cited in the file of this patent UNITED STATES PATENTS 33,400Overton Oct. 1, 1861 2,375,095 Flett May 1, 1945 2,557,062 Pickren- June19, 1951 2,573,862 Mim'ch et al Nov. 16, 1951

1. A FUNGICIDAL COMPOSITION ADAPTED WHEN MIXED WITH WATER TO FORM A WETSPRAY CONTAINING A DISPERSED SUSPENSION OF WATER-INSOLUBLE POLYVALENTMETAL SALT OF DODECYLBENZENE SULFONIC ACID AS AN ACTIVE FUNGICIDALINGREDIENT, SAID COMPOSITION COMPRISING A DRY, COMMINUTED, SUBSTANTIALLYFREE-FLOWING PHYSICAL MIXTURE OF A WATER-SOLUBLE DODECYLBENZENESULFONATE OF THE GROUP CONSISTING OF THE SODIUM ND POTASSIUM SULFONATESAND A WATER-SOLUBLE POLYVALENT METAL SALT OF THE GROUP CONSISTING OF THEWATER-SOLUBLE SALTS OF ZINC, COPPER, BARIUM, IRON, MANGANESE, MAGNESIUM,CALCIUM, LEAD AND MERCURY, SAID MIXTURE BEING PACKAGED FOR DISTRIBUTIONIN THE DRY STATE AND SAID SULFONATE AND SAID WATER-SOLUBLE METAL SALTHAVING APPROXIMATELY STIOCHIOMETRIC PROPORTIONS AND ADAPTED TO REACTWHEN ADDED TO WATER TO FORM A STABLE AQUEOUS SUSPENSION OF A FINELYDIVIDED DISPERSED PRECIPITATE OF SAID WATER-INSOLUBLE METAL SALT OFDODECYLBENZENE SULFONIC ACID.